Fuel cell storage system

ABSTRACT

The present invention includes an apparatus and method for volumetric and gravimetric storage of reactants and waste comprising: one or more reactant or fuel storage bladders; and one or more waste storage bladders, wherein the reactant or fuel storage bladders and the waste storage bladders form a stack of bladders, and the stack of bladders are interleaved between the reactant or fuel storage bladders and the waste storage bladders, such that both a volumetric and a gravimetric balance is maintained as reactant or fuel are used and the waste bladder is filled.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/511,800, filed May 26, 2017, the entire contents of which areincorporated herein by reference.

STATEMENT OF FEDERALLY FUNDED RESEARCH

This invention was made with government support under No.N00024-14-C-4083 awarded by United States Navy. The government hascertain rights in the invention.

TECHNICAL FIELD OF THE INVENTION

The present invention relates in general to the field of fuel cells, andmore particularly, to a novel fuel cell system.

BACKGROUND OF THE INVENTION

Without limiting the scope of the invention, its background is describedin connection with fuel cell systems.

U.S. Pat. No. 7,530,931, issued to Amendola, et al., is entitled“Hydrogen generator” and is said to teach a hydrogen generation systemthat includes a fuel container, a spent fuel container, a catalystsystem and a control system for generating hydrogen in a manner whichprovides for a compact and efficient construction while producinghydrogen from a reaction involving a hydride solution such as sodiumborohydride.

U.S. Pat. Nos. 7,220,290 and 6,534,033, issued to Amendola, et al., isentitled, “System for hydrogen generation” and is said to teach acomposition and method for storage and controlled release of hydrogen,specifically, the use of borohydride based solutions as a hydrogenstorage source and a catalyst system to release hydrogen therefrom.

U.S. Pat. Nos. 7,540,892 and 7,105,033, issued to Strizki, et al.,entitled “Hydrogen gas generation system” are said to teach a system forgenerating hydrogen gas that uses a volume exchange housing for thestorage of a fuel material that reacts to generate hydrogen gas and ahydrogen separation chamber, and includes a gas permeable membrane ormembranes that allow hydrogen gas to pass through the membrane whilepreventing aqueous solutions from passing through the membrane.

U.S. Pat. No. 7,083,657, issued to Mohring, et al. is entitled “Systemfor hydrogen generation” and is said to teach an improved system for thegeneration of hydrogen by contacting an aqueous solution of a metalhydride salt with a hydrogen generation catalyst, and the incorporationwithin the system of a recycle line of water condensed from the fluidproduct to the feed line to be contacted with the catalyst.

U.S. Pat. No. 6,932,847, issued to Amendola, et al., is entitled“Portable hydrogen generator” and is said to teach a hydrogen generationsystem includes a fuel container, a spent fuel container, a catalystsystem and a control system for generating hydrogen in a manner whichprovides for a compact and efficient construction while producinghydrogen from a reaction involving a hydride solution such as sodiumborohydride.

SUMMARY OF THE INVENTION

In one embodiment, the present invention includes an apparatus forvolumetric and gravimetric storage of reactants and waste of anintegrated fuel cell system comprising: one or more reactant or fuelstorage bladders; and one or more waste storage bladders, wherein thereactant or fuel storage bladders and the waste storage bladders form astack of bladders, and the stack of bladders are interleaved between thereactant or fuel storage bladders and the waste storage bladders, suchthat both a volumetric and a gravimetric balance is maintained asreactant or fuel are used and the waste bladder is filled. In oneaspect, the bladders are plastic, polymer, rubber, thermoplastic,composite, silicone, fiberglass, or carbon fiber. In another aspect, thestack of bladders is conformal with a container that at least partiallyencloses the stack of bladders. In another aspect, the reactant or fuelstorage bladders and/or the waste storage bladders are selected from amaterial capable of storing corrosive, acid, basic, external pressure,internal pressure, cold, heat, UV protected, chemical solvents, organicsolvents, mineral solvents, radioactive elements or compounds, oroxidation. In another aspect, the reactant or fuel storage bladdersand/or the waste storage bladders further comprise a liner, wherein theliner is selected from polytetrafluoroethylene, metal, plastic, carbonfiber, glass fiber, a material substantially impermeable to gases, amaterial substantially permissive of gas diffusion, or selective gasdiffusion. In another aspect, the reactant or fuel storage bladdersand/or the waste storage bladders area at least partially rigid. Inanother aspect, the reactant or fuel storage bladders and/or the wastestorage bladders are defined further as comprising a heat sink. Inanother aspect, the apparatus further comprises a reinforcing materialin, within, or on the reactant or fuel storage bladders and/or the wastestorage bladders selected from carbon fiber, metal, polymeric, nylon, apara-aramid synthetic fiber, a natural fiber, wood, or bamboo. Inanother aspect, the reactant or fuel storage bladders and/or the wastestorage bladders is cylindrical, ovoidal, pancake shaped, accordionshaped, tubular, polygonal, cubic, spherical, pyramidal, rhomboid,conical, half-cylinders that sandwich an expandable bladder, vessel, orcontainer. In another aspect, the reactant or fuel storage bladdersand/or the waste storage bladders further comprise one or more baffleswithin the reactant or fuel storage bladders and/or the waste storagebladders. In another aspect, the apparatus further comprises one or moreflow restrictors between the two or more reactant or fuel storagebladders and/or the two or more waste bladders to dampen fluid movementin the two or more reactant or fuel storage bladders and/or the two ormore waste bladders during operation. In another aspect, the reactantstorage bladders comprise, independently, a NaBH₄ storage bladder and aH₂O₂ storage bladder. In another aspect, a reactant for use in the fuelcell system is a metal-hydride. In another aspect, a reactant for usewith the present invention is selected from at least one of NaBH₄,LiBH₄, KBH₄, Ca(BH₄)₂, or Mg(BH₄)₂.

In another embodiment, the present invention includes a method ofmaintaining a volumetric and gravimetric balance in a closed systemcomprising: providing two or more reactant or fuel storage bladders andone or more waste bladders; and forming a stack of bladders byinterleaving the two or more storage or fuel storage bladders and theone or more waste bladders, wherein a volumetric and a gravimetricbalance is maintained as reactant or fuel is used and the waste bladderis filled. In one aspect, the method further comprises connecting thetwo or more the reactant or fuel storage bladders to a reactor inlet anda fuel cell, and connecting the reactor fuel outlet and/or a fuel celloutlet to the one or more waste bladders and adapting the closed systemto fit into an unmanned underwater vehicle. In another aspect, thebladders are plastic, polymer, rubber, thermoplastic, composite,silicone, fiberglass, or carbon fiber. In another aspect, the stack ofbladders is conformal with a container that at least partially enclosesthe stack of bladders. In another aspect, the reactant or fuel storagebladders and/or the waste storage bladders are selected from a materialcapable of storing corrosive, acid, basic, external pressure, internalpressure, cold, heat, UV protected, chemical solvents, organic solvents,mineral solvents, radioactive elements or compounds, or oxidation. Inanother aspect, the reactant or fuel storage bladders and/or the wastestorage bladders further comprise a liner, wherein the liner is selectedfrom polytetrafluoroethylene, metal, plastic, carbon fiber, glass fiber,a material substantially impermeable to gases, a material substantiallypermissive of gas diffusion, or selective gas diffusion. In anotheraspect, the reactant or fuel storage bladders and/or the waste storagebladders area at least partially rigid. In another aspect, the reactantor fuel storage bladders and/or the waste storage bladders are definedfurther as comprising a heat sink. In another aspect, the method furthercomprises a reinforcing material in, within, or on the reactant or fuelstorage bladders and/or the waste storage bladders selected from carbonfiber, metal, polymeric, nylon, a para-aramid synthetic fiber, a naturalfiber, wood, or bamboo. In another aspect, the reactant or fuel storagebladders and/or the waste storage bladders is cylindrical, ovoidal,pancake shaped, accordion shaped, tubular, polygonal, cubic, spherical,pyramidal, rhomboid, conical, half-cylinders that sandwich an expandablebladder, vessel, or container. In another aspect, the reactant or fuelstorage bladders and/or the waste storage bladders further comprise oneor more baffles within the reactant or fuel storage bladders and/or thewaste storage bladders. In another aspect, the method further comprisesproviding one or more flow restrictors between the two or more reactantor fuel storage bladders and/or the one or more waste bladders to dampenfluid movement in the two or more reactant or fuel storage bladdersand/or the one or more waste bladders during operation. In anotheraspect, the method further comprises maximizing a fill volume and evendistribution of one or more reactants by pre-inflating the two or morereactant or fuel storage bladders with gas. In another aspect, themethod further comprises filling the two or more reactant or fuelstorage bladders with reactants while the gas is removed from aheadspace via a vent in the two or more reactant or fuel storagebladders at the same volumetric rate, thereby maintaining an optimumform for the bladder. In another aspect, a reactant for use in the fuelcell system is a metal-hydride. In another aspect, a reactant for usewith the present invention is selected from at least one of NaBH₄,LiBH₄, KBH₄, Ca(BH₄)₂, or Mg(BH₄)₂.

In yet another embodiment, the present invention includes a method ofoperating an underwater vehicle comprising: an underwater vehiclecomprising one or more reactant or fuel storage bladders; andmaintaining a volumetric and gravimetric balance in a closed system by:providing two or more the reactant or fuel storage bladders and one ormore waste bladders; and forming a stack of bladders by interleaving thetwo or more storage or fuel storage bladders and the one or more wastebladders, wherein a volumetric and a gravimetric balance is maintainedas reactant or fuel is used and the waste bladder is filled.

Yet another embodiment, the present invention includes a gas vent foruse with a bladder system comprising: a perforated tube that extendsinside a bladder; a gas permeable film that surrounds the perforatedtube and covers substantially all of the perforation in the perforatedtube; a pass-through fitting that is attachable to a wall of thebladder, wherein gas in the bladder traverses the gas permeablemembrane, though the perforations in the tube and through thepass-through fitting to exit the bladder. In one aspect, thepass-through fitting has a 30, 45, 60, 75, 90, 105, 120, 135, 150, or165 degree angle. In another aspect, the gas permeable membrane isselected to only permit certain types of gases to enter the perforatedtube and/or to prevent liquids from exiting the bladder. In anotheraspect, the gas permeable membrane is hydrophobic. In another aspect,the perforated tube is a self-supporting tube, and/or is supported by awire or stiffener inserted in the perforated tube that providesmechanical rigidity to the perforated tube and can be shapedaccordingly. In another aspect, the gas vent further comprises apressure valve connected between the perforated tube and an outlet ofthe gas vent to prevent escape of a gas until a certain internalpressure is reached within the bladder. In another aspect, the gas venteliminates the need for head space in a bladder for gas, while retainingliquids.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the features and advantages of thepresent invention, reference is now made to the detailed description ofthe invention along with the accompanying figures and in which:

FIG. 1 is a graph that shows the solubility of aqueous sodiumborohydride and sodium borate as a function of temperature.

FIG. 2 is a graph that shows the effective gravimetric and volumetricstorage of hydrogen vs. NaBH₄ wt % at 20° C.

FIG. 3 is a graph that shows theoretical NaBH₄ reactor outlet parametersvs. back-pressure assuming inlet conditions of 20 wt % NaBH₄, 20 C, 100%hydrolysis reaction conversion and adiabatic conditions.

FIG. 4 is a graph that presents the stoichiometric and thermodynamicallycompensated relationship between the NaBH₄ feed concentration and NaBO₂outlet concentration for an adiabatic reactor operating at 60 psig.

FIG. 5 is a diagram that shows the water management between the varioussub-systems in terms of moles of water.

FIG. 6 is a graph that shows NaBH₄ and NaBO₂ wt % as a function of molesof water (in reference to Equations 2-8).

FIG. 7 is a graph that shows NaBO₂ concentration at the storage vesseland NaBH₄ diluted concentration at the reactor inlet as a function ofNaBH₄ storage concentration.

FIG. 8 is a block diagram that shows a system for level water managementof the present invention.

FIG. 9 is a block diagram of the fuel intra-subsystem water recoverytechnique. Two phase separators and a heat exchanger/condenser are usedto separate the un-usable borate byproduct from the usable condensedproduct water.

FIG. 10 is a block diagram of the H₂O₂ intra-subsystem water recoverytechnique.

FIG. 11 is a diagram that shows multiple fluid containers with flowrestrictors between the multiple fluid containers that dampen fluidmovement during pitch and/or roll maneuvers.

FIG. 12 is a diagram which shows that adding relatively large valueresistance to parallel flow lines reduces the effect of minordifferences.

FIG. 13 is a diagram that shows an asymmetric layout results inhorizontal CG shift if reactants are not of similar density and/orvolume.

FIG. 14 is a diagram that shows a “pancake” bladder configuration withalternating reactant/waste pairs

FIG. 15 is a diagram that shows side-by-side bladder configuration withreactant in purple and waste in orange (exploded view). Gray cylinder isfor bladder installation and shows conduit passing through center.

FIG. 16 is a cross-sectional side view of a perforated tube vent withinternal stiffener can be installed through a small port and configuredfor best access to high points in the container for gas removal.

FIG. 17 shows a diagram of one embodiment of the hydrogen generator ofthe present invention.

FIG. 18 shows an example of a reactor design for generating H₂ For usewith the present invention.

FIG. 19 shows an example of a fluid management between fuel/waterstorage and hydrolysis reactor via the conduit system for use with thepresent invention.

FIG. 20A shows an example of a reactor water recovery by phaseseparation of the present invention.

FIG. 20B shows an example of a reactor water recovery by phaseseparation of the present invention.

FIG. 21A shows an example of a water reservoir system for use with thepresent invention.

FIG. 21B shows an example of a float type continuous level sensor foruse with the present invention.

FIGS. 22A and 22B are graphs that show the product as a weight percentwt % of the NaBH₄ and NaBO₂, in relation to: FIG. 22A the wt % ofreactant NaBH₄, and in FIG. 22B the Wt % of the reactant H₂O₂.

DETAILED DESCRIPTION OF THE INVENTION

While the making and using of various embodiments of the presentinvention are discussed in detail below, it should be appreciated thatthe present invention provides many applicable inventive concepts thatcan be embodied in a wide variety of specific contexts. The specificembodiments discussed herein are merely illustrative of specific ways tomake and use the invention and do not delimit the scope of theinvention.

To facilitate the understanding of this invention, a number of terms aredefined below. Terms defined herein have meanings as commonly understoodby a person of ordinary skill in the areas relevant to the presentinvention. Terms such as “a”, “an” and “the” are not intended to referto only a singular entity, but include the general class of which aspecific example may be used for illustration. The terminology herein isused to describe specific embodiments of the invention, but their usagedoes not delimit the invention, except as outlined in the claims.

Effective Gravimetric and Volumetric Storage of Aqueous NaBH₄.

Typically, fuel cells are used for low mass and/or low volumeapplications. This is primarily due to the high relative efficiency ofthe fuel cell and separation of the reactants from the power generationdevice (fuel cell). Specifically, proton exchange membrane (PEM) fuelcells require hydrogen gas as a fuel. Effective mass and volume storageof the hydrogen is currently a major barrier for the viability of fuelcells. Chemical hydrides, which store hydrogen in a chemical compoundfor effective mass and volumetric storage, have become a promisingsolution. A great deal of investigation has been performed on SodiumBorohydride (NaBH₄) specifically due to its high gravimetric hydrogen wt%, purity, and the high stability and solubility of the compound in anaqueous solution. NaBH₄ reacts with water to form hydrogen gas andBorate while releasing heat (Equation 1).

NaBH₄+(2)H₂O→NaBO₂+(4)H₂+212 kJ  Equation 1

As can be seen by the reaction, the ideal ratio of NaBH₄ to water is 1:2moles respectively, or 51 wt % of NaBH₄. Since NaBH₄ may be stored witha relatively high stability as an aqueous solution, catalytic reactorsare used to generate the hydrogen on demand. FIG. 1 is a graph thatshows the solubility of aqueous sodium borohydride and sodium borate asa function of temperature.

However, the solubility of the byproduct, borate, is significantly lesssoluble than the reactant, NaBH₄ (FIG. 1). To make matters worse, wateris consumed during the reaction, reducing the amount of water tosolubilize the byproduct. If the maximum solubility is exceeded duringthe reaction inside the reactor, solid crystals are formed whichphysically damage the reactor due to clogging and catalyst erosion.Therefore, the maximum solubility of the reactant, NaBH₄, can never berealized in storage as the solubility of the byproduct, Borate, limitsthe NaBH₄ feed concentration. This is problematic since the goal ofusing NaBH₄ in the first place is to increase the gravimetric andvolumetric storage of hydrogen. FIG. 2 is a graph that shows theeffective gravimetric and volumetric storage of hydrogen vs. NaBH₄ wt %at 20° C.

The present inventors have developed specific solutions to increase theeffective storage concentration of aqueous NaBH₄ that addresses theissue of reduced NaBO₂ solubility.

Solution A—Back Pressure Regulator (Affects all NaBH₄ Reactors).

Even though fully soluble NaBH₄ solutions are fed into the reactor, thebyproduct, NaBO₂, can crash out of solution, crystallizing and in theprocess damaging the reactor due to the limited solubility. Solubilityof the byproduct is dependent upon the amount of liquid water availableand the temperature of the system (FIG. 1). Although the solubility ofthe byproduct cannot be changed, the temperature and available liquidwater fraction may be somewhat controlled. Most often, the reactor willoperate under adiabatic conditions to simplify the reactor design byeliminating the necessity of a cooling system. In this adiabatic case,the outlet temperature of the reactor may be calculated from the inlettemperature and system pressure alone, assuming complete reaction (FIG.3). Therefore, assuming a room temperature inlet, only the temperatureand thus back-pressure of the reactor affects the solubility of thebyproduct. During operation, increasing the pressure increases thetemperature and the available liquid water, both improving thesolubility of the byproduct (NaBO₂). To overcome this problem, which wasverified both theoretically (via thermodynamics) and experimentally, thepresent inventors added a back-pressure regulator downstream of thereactor. This physical addition insures that the reaction takes place atan elevated pressure, regardless of flow rate or H₂ production rate,reducing the concentration of the byproduct, NaBO₂, thus substantiallyincreasing reactor lifetime. FIG. 3 is a graph that shows theoreticalNaBH₄ reactor outlet parameters vs. back-pressure assuming inletconditions of 20 wt % NaBH₄, 20 C, 100% hydrolysis reaction conversionand adiabatic conditions.

Solution B—Pre-Heating Fluid with HX (Effects all NaBH₄ Reactors).

As shown previously in FIG. 3, increasing the pressure will increase theoutlet temperature. However, the increased outlet temperature does notdirectly solve the byproduct solubility issue. The steady stateoperational reactor will have a thermal gradient from the inlettemperature to the outlet temperature. Therefore, even though the borateat the outlet of the reactor will be fully soluble, some reaction,forming borates, will occur near the colder inlet of the reactor. Theexistence of borates at these localized cold spots can locally damagethe reactor with a cumulative effect. Eventually, the reaction zone willshift from the inlet of the reactor towards the outlet as the cold spotsand thus degradation propagates through the reactor. Under theseconditions, the reactors life will be quite short. However, thisdegradation mechanism may be significantly reduced with intelligentcontrol of the inlet feed concentration and temperature. FIG. 4 is agraph that shows the relationship between NaBH₄ feed concentration andNaBO₂ outlet concentration for an adiabatic reactor operating at 60psig. If the inlet temperature is increased from 20 to 40° C., thelimiting feed concentration of NaBH₄ may be increased from 10.8 to 14.6wt % respectively, while maintaining full solubility of the boratebyproduct at inlet cold spots.

FIG. 4 is a graph that shows the stoichiometric and thermodynamicallycompensated relationship between the NaBH₄ feed concentration and NaBO₂outlet concentration for an adiabatic reactor operating at 60 psig. Alsoillustrated is the solubility limit of NaBO₂ at both 20 and 40° C. Thisgives a surprising insight that the NaBH₄ feed concentration may beincreased substantially while maintaining full solubility of the NaBO₂if the inlet temperature is increased. To overcome this problem, whichwas verified both theoretically (via thermodynamics) and experimentally,the present inventors insulated and preheated the reactor feed streamwith electric heaters on startup and a novel integrated reactor heatexchanger during steady state operation. These physical additions insurethat the NaBO₂ byproduct is fully soluble at localized cold spots duringstartup and steady state operation, thus substantially increasingreactor lifetime.

Solution C—System Level Water Management.

Storing NaBH₄ at elevated concentrations, or even in the solid form,would result in increased gravimetric and volumetric energy storage.However, above the ideal stoichiometric 51 wt %, not enough water isavailable for the reaction. Additionally, water limitations may causethe byproduct to crystallize in the reactor or in the waste storagevessel making it difficult to remove, requiring even lower feedconcentrations (see FIG. 4). Many others have already investigated theidea of using wastewater from other parts of the system (for examplefuel cell product water) for diluting the NaBH₄ either prior to or afterthe reactor. While the skilled artisan would expect the implementationof this water utilization design to become cumbersome and evendangerous, the present inventors demonstrate herein the advantages ofthis configuration and overcoming those challenges. The presentinventors recognized the need for additional water in the NaBH₄hydrolysis reaction, determined that a system level water managementstrategy is necessary. As such, the present inventors evaluated severalfuel and oxidizer combinations for a PEM fuel cell and determined thatthe specific combination of NaBH₄ and H₂O₂ offers an attractive couplebased specifically on water management. FIG. 5 is a diagram that showsthe water management between the various sub-systems in terms of molesof water. In FIG. 5, the system level water management strategy is shownas flow chart 10, which shows an oxidizer 12 from which the OX productwater (4+y) H₂O is combined with the fuel 14. The FC product water isobtained from Fuel Cell 14, with a reactant storage 18, in communicationwith the fuel 16. The waste return for the fuel 16 is L (x−2) H₂O, whilethe reactant storage 18 provides aqueous sodium borohydride thatsupplies (x) H₂O. The Reactant storage 18 is also in communication withoxidizer 12, to which is provides an aqueous peroxide supply of (y) H₂O.

Equations 2-4 show the system balanced stoichiometric chemical reactionsfor each step of the overall system. Equation 2 represents the NaBH₄fuel hydrolysis reaction, which includes parameter “x” for water used tosolubilize the reactants and products. Specifically, “x” is used toquantify the amount of water used to solubilize the NaBH₄ during storageand “y” is used to quantify the water used to dilute the hydrogenperoxide during storage. It should also be noted that 212 kJ of heat isreleased during this reaction. Equation 3 represents the hydrogenperoxide decomposition reaction. 392 kJ of heat is released during thisreaction. Equation 4 represents the PEM fuel cell reaction, whichreleases a total energy of 1143 kJ. However, it should be noted thatapproximately half of this energy will be released as heat whereas theother half will be transformed into electrical energy by the fuel cellassuming that the fuel cell is 50% efficient based on total availableenthalpy.

$\begin{matrix}{\mspace{79mu} {{{Fuel}\mspace{14mu} {Reaction}}\left. {{NaBH}_{4} + {(x)H_{2}O_{(l)}}}\rightarrow{{NaBO}_{2} + {(4)H_{2}} + {\left( {x - 2} \right)H_{2}O_{(l)}} + {212\mspace{14mu} {{kJ}_{heat}.}}} \right.}} & {{Equation}\mspace{14mu} 2} \\{\mspace{79mu} {{{Oxidizer}\mspace{14mu} {Reaction}}\begin{matrix}{{\begin{matrix}\left. {{(4)H_{2}O_{2{(l)}}} + {(y)H_{2}O_{(l)}}}\rightarrow \right.\end{matrix}\left( {4 + y} \right)H_{2}O_{(l)}} + {(2)O_{2}} + {392\mspace{14mu} {{kJ}_{heat}.}}}\end{matrix}{{\begin{matrix}\left. {{(4)H_{2}O_{2{(l)}}} + {(y)H_{2}O_{(l)}}}\rightarrow{{\left( {4 + y} \right)H_{2}O_{(l)}} +} \right.\end{matrix}\mspace{14mu} (2)O_{2}} + {392\mspace{14mu} {{kJ}_{heat}.}}}}} & {{Equation}\mspace{14mu} 3} \\{\mspace{79mu} \left. {{{Fuel}\mspace{14mu} {Cell}\mspace{14mu} {{Reaction}(4)}H_{2}} + {(2)O_{2}}}\rightarrow{{(4)H_{2}O_{(l)}} + {572\mspace{14mu} {kJ}_{heat}} + {572\mspace{14mu} {{kJ}_{electrical}.}}} \right.} & {{Equation}\mspace{14mu} 4} \\{\mspace{79mu} {{{Overall}\mspace{14mu} {System}\mspace{14mu} {Reaction}}{{\begin{matrix}\left. {{NaBH}_{4} + {(4)H_{2}O_{2{(l)}}} + {\left( {x + y} \right)H_{2}O_{(l)}}}\rightarrow{{NaBO}_{2} +} \right.\end{matrix}\left( {6 + x + y} \right)H_{2}O_{(l)}} + {1176\mspace{14mu} {kJ}_{heat}} + {572\mspace{14mu} {{kJ}_{electrical}.}}}}} & {{Equation}\mspace{14mu} 5} \\{{{Fuel}\mspace{14mu} {reaction}\mspace{14mu} {with}\mspace{14mu} {full}\mspace{14mu} {water}\mspace{14mu} {utilization}\mspace{14mu} \left( {{from}\mspace{14mu} {Oxidizer}\mspace{14mu} {and}\text{}{fuel}\mspace{14mu} {cell}} \right)}\left. {{NaBH}_{4} + {\left( {8 + x + y} \right)H_{2}O_{(l)}}}\rightarrow{{NaBO}_{2} + {(4)H_{2}} + {\left( {6 + x + y} \right)H_{2}O_{(l)}} + {212\mspace{14mu} {{kJ}_{heat}.}}} \right.} & {{Equation}\mspace{14mu} 6} \\{{{Fuel}\mspace{14mu} {byproduct}\mspace{14mu} {concentration}\mspace{11mu} {assuming}\mspace{14mu} {full}\mspace{14mu} {water}\mspace{14mu} {utilization}}{{{Wt}\mspace{14mu} \% \mspace{14mu} {NaBO}_{2{({{aq}.})}}} = {\frac{{NaBO}_{2}}{{NaBO}_{2} + {\left( {6 + x + y} \right)H_{2}O}} = {\frac{65.8}{65.8 + {\left( {6 + x + y} \right)18}}{Wt}\mspace{14mu} {\%.}}}}} & {{Equation}\mspace{14mu} 7} \\{{{Fuel}\mspace{14mu} {reactor}\mspace{14mu} {feed}\mspace{14mu} {concentration}\mspace{14mu} {assuming}\mspace{14mu} {full}\mspace{14mu} {water}}\text{}{utilization}{{{Wt}\mspace{14mu} \% \mspace{14mu} {NaBH}_{4{({{aq}.})}}} = {\frac{{NaBH}_{4}}{{NaBH}_{4} + {\left( {8 + x + y} \right)H_{2}O}} = {\frac{37.8}{37.8 + {\left( {8 + x + y} \right)18}}{Wt}\mspace{14mu} {\%.}}}}} & {{Equation}\mspace{14mu} 8} \\{{{Overall}\mspace{14mu} {System}\mspace{14mu} {Efficiency}\mspace{14mu} {based}\mspace{14mu} {on}\mspace{14mu} {total}\mspace{14mu} {Enthalpy}\mspace{14mu} ({HHV})}{\eta_{electrical} = {\frac{{Energy}_{electrical}}{{Energy}_{Total}} = {\frac{572\mspace{14mu} {kJ}}{{572\mspace{14mu} {kJ}} + {1176\mspace{14mu} {kJ}}} = {33{\%.}}}}}} & {{Equation}\mspace{14mu} 9}\end{matrix}$

If Equation 2-4 are condensed into one overall system equation, theresult is Equation 5 which may be used to calculate the final NaBO₂storage concentration assuming that all of the product water is mixedwith the waste (Equation 7). However, if this product water is mixedwith the NaBH4 fuel prior to the reactor feed, Equation 2 turns intoEquation 6, which may be used to calculate the reactor feedconcentration (Equation 8). Another interesting observation fromEquation 5 is that the overall system efficiency based off of totalavailable enthalpy is ˜33% (Equation 9).

Although pure 100 wt % H₂O₂ is available, shipping and safetyregulations can limit the practical concentration of H₂O₂ to 59 wt %.Therefore, 59 wt % H₂O₂ was used for the following calculations as itrepresents one practical maximum concentration. The skilled artisan willrecognize, using the teachings herein, that the wt % of the H₂O₂ can bevaried based on the equations above to use any wt % necessary to achievethe required reactant. For example, the wt % of H₂O₂ can be used at 20,30, 40, 50, 55, 59, 60, 61, 62, 64, 65, 70, 75, 80, 85, 90, 95, or 100wt % and the moles can be varied accordingly. For these calculations,with 59 wt % H₂O₂, y=1.31 moles, which was used as a constant. Thisresults in the only variable in the relations being x. Therefore, thefinal NaBO₂ concentration may be plotted as a function of x (or storageNaBH₄ wt %). FIG. 6 is a graph that shows NaBH₄ and NaBO₂ wt % as afunction of moles of water (in reference to Equations 2-8), y=1.31. FIG.7 is a graph that shows NaBO₂ concentration at the storage vessel andNaBH₄ diluted concentration at the reactor inlet as a function of NaBH₄storage concentration. All the product water from the fuel cell and H₂O₂reaction can be used for the fuel reaction. Based on this relation,enough water is theoretically available even if solid anhydrous NaBH₄ isstored. At 20° C., the solubility of NaBH₄ is ˜35 wt %, therefore enoughwater is available to dissolve all of the solid NaBH₄ into an aqueoussolution for fluidic delivery to the fuel reactor. If a fully solublewaste product is desired at 20° C., 21 wt % NaBO₂ must be maintainedwhich limits the NaBH₄ storage to 26 wt %, y=1.31.

Both NaBH₄ and NaBO₂ concentrations may be seen in FIG. 6 as a functionof “x” (Moles of water stored with NaBH₄) and in FIG. 7 as a function ofNaBH₄ weight percent (wt %) used for storage. Both FIGS. 6 and 7 assumethat all the product water from the fuel cell and H₂O₂ reaction is usedfor the fuel reaction (full water utilization). Based on this relation,enough water is theoretically available even if solid anhydrous NaBH₄ isstored. At 20° C., the solubility of NaBH₄ is ˜35 wt %, therefore enoughwater is available to dissolve all of the solid NaBH₄ into an aqueoussolution for fluidic delivery to the fuel reactor. If a fully solublewaste product is desired at 20° C., 21 wt % NaBO₂ must be maintainedwhich limits the NaBH₄ storage to 26 wt %.

FIG. 8 shows a block diagram of the system for level water management 30of the present invention. The oxidizer 12 that provides OX product waterand the fuel cell 14 that provides fuel cell product water, aredepicted. These connect to a fuel subsystem 32, which is a commonrecaptured water reservoir 34, which is used account for deliverytransients. This allows for a continuous flow of water to be deliveredto the reactor 36, avoiding transient concentration shifts. The rate ofwater dilution is controlled with a specialized water level feedbackloop, which prevents the water reservoir from emptying or overfillingwhile insuring a minimum threshold fuel dilution and full system levelwater utilization. A specialized mixing chamber 38 is also used toreduce the possibility of concentrated NaBH₄ solutions from entering thereactor. The reactant, e.g., concentrated NaBH₄, is obtained from thereactant storage containers 40, one of which can provide hydrogenperoxide 42.

The present inventors obtained full water utilization with theNaBH₄/H₂O₂ couple via unique water recapture, storage and subsequentdilution strategies. Custom phase separators are used to capture theliquid product water from the oxidizer reactor, fuel cell anode and fuelcell cathode safely without permitting any entrained gas. This capturedwater is then delivered to a temporary water storage reservoir toaccount for system transients. The water is then pumped from the systemlevel water reservoir and mixed with the fuel stream prior to deliveryto the fuel reactor. The rate of water dilution is controlled with aspecialized feedback loop, which prevents the water reservoir fromemptying or overfilling while insuring a minimum threshold fuel dilutionand full system level water utilization.

Solution D—Fuel/Oxidizer Intra-Subsystem Water Recovery.

Although utilizing this unique system level water management approach(discussed previously) theoretically yields enough liquid water to fullysolubilize solid anhydrous NaBH₄, this precise water balance isdifficult to achieve in practice. These difficulties are a result ofsystem transients, thermal imbalances and practical accuracies/controlsof flow meters and pumps (especially at very small volumetric rates).

Any additional water that may be recaptured and used to dilute the feedstreams is useful for both the fuel and oxidizer reactors. As discussedpreviously, reducing the fuel reactor feed concentration reduces thechances of borate (by-product) precipitation, which leads to reactordamage and diminished lifetime. However, the hydrogen peroxide reactormay also benefit from reduced inlet concentrations with increasedlifetimes.

One of the primary H₂O₂ reactor degradation mechanisms is contaminationfrom the stabilizers used in the H₂O₂ itself. Lack of available liquidwater throughout the H₂O₂ reaction can lead to precipitation of thestabilizer (commonly Potassium or Sodium Stannate) onto the catalyst,thus reducing catalytic activity. Similar to the fuel reaction, moreliquid water is available when utilizing lower concentrations of H₂O₂and when running at higher pressures with a BPR. Additionally, the H₂O₂reaction can see localized and transient water shortages (caused by flowpulsations) again leading to stagnation and precipitation of thestabilizer. For these reasons, adding additional water to the inlet ofthe H₂O₂ reactor and diluting the H₂O₂ concentration results in longerlifetimes.

However, due to the need for additional water by both the fuel andoxidizer subsystems, a decision must be made on which subsystem needswhat allocations of water. This decision primarily depends on therelative storage concentrations of the NaBH₄ and H₂O₂ solutions.

However, two unique intra-subsystem water recovery techniques may beused by both subsystems simultaneously without affecting the overallsystem level water balance.

For the fuel subsystem, additional product water was obtained byimplementing a two-stage phase separation (see FIG. 9). The first stageof phase separation occurs at high temperature (>100° C.). As usedherein, high temperature in the hydrogen/liquid separator is >100° C.,for example 105, 110, 115, 120, 125° C. This removes the solubilizedbyproduct (borate solution) for subsequent waste storage. Saturatedhydrogen gas then travels out of the top of the high temperature phaseseparator through a heat exchanger, cooling and condensing the saturatedvapor down to about 60° C. As used herein, low temperature in thehydrogen/liquid separator is 50 to 90° C., for example 55, 60, 65, 70,75, 80, 85, or 90° C. The two phase liquid/gas mixture then enters thelow temperature phase separator where the liquid water may be capturedand drained into a common liquid water storage tank (common to the othersources of recaptured water previously discussed). From there the watercan be feed continuously back into the fuel reactor, thus furtherreducing the reactor inlet concentration. FIG. 9 is a block diagram 50of the fuel intra-subsystem water recovery technique. Two phaseseparators and a heat exchanger/condenser are used to separate theun-usable borate byproduct from the usable condensed product water. Areactant, depicted in this example as concentrated NaBH₄ is provided viaa delivery pump 52, which reactant enters reactor 54. Water produced atthe reactor 54 enters a high temperature phase separator 56, which issaturated with hydrogen and enters a heat exchanger/condenser 58. Thesaturated hydrogen and condensed water then enters a low temperaturephase separator 60, which separates the product hydrogen gas 62 from therecovered condensed water. The recovered condensed water enters therecovered liquid water storage reservoir 64, which can be pumped backinto the reactor at recovered water delivery pump 66. The hightemperature phase separator 56, separates the saturated hydrogen fromthe liquid waste, which is stored in liquid waste storage 68.

Within the oxidizer subsystem, a unique water recirculation loop wasused that is fundamentally different than the fuel subsystems (see FIG.10). Since the H₂O₂ decomposition reaction has no products other thanoxygen gas and water, the two-phase separator approach is not needed.The product stream from the reactor is fed directly into the heatexchanger where additional water vapor is condensed at ˜60° C.Subsequently the two phase mixture is separated so that the liquid watermay be both delivered to the fuel subsystem (as previously described)and re-circulated to the H₂O₂ reactor for additional dilution. Althoughthe fuel intra-subsystem water recovery rate is limited by the enthalpyreleased by the hydrolysis reaction (this limits the amount ofcondensate recovered), the H₂O₂ re-circulation rate is theoreticallyunlimited and has no net effect on the rate of product water deliveredto the fuel subsystem. This is realized since any liquid water removedfrom the phase separator and delivered to the reactor eventually ends upback in the phase separator. This allows the system to accuratelycontrol the H₂O₂ concentration at the reactor inlet without affectingthe overall system level water balance. FIG. 10 is a block diagram 70 ofthe H₂O₂ intra-subsystem water recovery technique. A concentrated H₂O₂is delivered by H₂O₂ pump 72, which concentrated H₂O₂ enters reactor 54.The reactor 54 generates a saturated oxygen and liquid water mixture,which enter heat exchanger/condenser 74. A saturated oxygen andadditional condensed water exits the heat exchanger/condenser 74 andenters a low temperature phase separator 76. A product oxygen gas 78 isproduced by the low temperature phase separator 76 with the net productliquid water delivered to the fuel subsystem 80. The recovered condensedwater can be re-circulated liquid water that enters the re-circulatedliquid water delivery pump 82, which fees the reactor 54. In onenon-limiting example, the present inventors used the two aforementionedintra-subsystem water recovery techniques to further reduce both theNaBH₄ and H₂O₂ reactor inlet concentrations, significantly increasingreactor lifetime.

Bladder Manifold Management.

When aqueous NaBH₄ is selected as the hydrogen source of fuel for apower system, there are typically constraints on system mass and/orvolume that lead to this selection because of its high gravimetrichydrogen wt %. In such an application, the oxygen source may beconcentrated hydrogen peroxide (H₂O₂). NaBH₄ produces NaBO₂ as waste,and H₂O₂ produces water. In some cases, it is advantageous to retain thewaste within the system until it is refueled, and to do so whilelimiting any shifts in center of gravity (CG) of the system.

In the case of case of underwater vehicles, for example, maintainingconstant system buoyancy may be critical to vehicles without activeballast control, and retaining all waste products in a closed system isthe most straightforward method of doing so. Additionally, CG shifts canresult in unacceptable changes in vehicle attitude, leading to reducednavigation control. In this case, it is important to have confidencethat the power system CG will stay within a narrow range as reactantsare converted to waste.

Collapsible bladders for reactant and waste storage allow generatedwaste to fill the void left by consumed reactants. Their flexibilityallows for adaptation to unique spaces and volumetric reactant-to-wasteconversion ratios that deviate from 1:1. If the waste is more dense thanthe reactants consumed, it will simply fill its bladder more slowly thanthe reactant bladders collapse, or vice-versa. A rigid separationbetween the two volumes would not allow this expansion/contractiondifferential without additional compensating mechanisms. Although theirflexibility is advantageous, collapsible bladders can result inunacceptable CG shifts if they do not fill or drain in a uniform orsymmetric manner. Solutions to control or influence bladderfilling/expansion and draining/collapse are discussed below.

Solution A—Restricted Fluid Movement Using Multiple Bladders as Baffles.

When the energy system changes pitch or roll attitude, gravity will tendto cause the fluids to shift to lower space if any room is available.Additionally, differences in densities between the fluids (reactants andwaste) can cause them to shift during system pitch and/or roll so thatless dense fluids move toward the new high point and more dense fluidsmove toward the new low point. In a vehicle, this means the CG shiftsalong the length of the vehicle, exaggerating pitch control inputs.

Baffles spaced along the direction of attitude (i.e., along the lengthof the vehicle for pitched maneuvers) within the storage volume willslow down fluid shifting during short-term pitch or roll maneuvers,dampening the resultant CG shift. One implementation of storagecontainers that effectively baffles fluid flow is to divide the volumeinto multiple containers with flow restrictors between them. One exampleis to use multiple bladders connected in parallel to permit the contentsto move between bladders, but with orifices or long lengths of smalldiameter tubing to slow that movement down to acceptable levels. FIG. 11is a diagram that shows a restricted fluid movement using multiplebladders as baffles system 100, that shows multiple fluid containers 102a-c, with flow restrictors 104 a,b between them to dampen fluid movementduring pitch and/or roll maneuvers.

Solution B—Even Distribution of Flow Through a Manifold Using FlowRestrictions.

Flow from a single source through parallel lines in a system will beinversely proportional to the relative resistance to flow in each line.In order to fill multiple containers evenly, the flow resistance fromthe source to each container must be identical. Any variations willresult in uneven filling. With open containers or rigid containershaving fluid communication between containers at the head and drain (topand bottom), levels will even out over time after filling is complete.With collapsible containers having fluid communication at the head anddrain, the fluid level will tend to seek its own, but the container sizewill not necessarily adjust, so that one container may remain expandedmore than another if it receives more flow during filling.

Perfectly identical flow resistance in parallel is impossible toachieve, and differences may be significant in the case of collapsiblecontainers because of constrictions or differences in resistance toexpansion. Since the differences in flow are inversely proportional toflow resistance, one method to minimize differences is to place a largevalue of identical flow restriction in each parallel path. This reducesthe relative impact of minor differences in resistance. For example, iftwo parallel lines had relative resistance of 1 and 1.5, the first linewould receive 60% of flow and the other would receive 40%, a 20%difference. By adding resistance of 10 to each line, the lines wouldreceive 51% and 49% each, only a 2% difference. For collapsiblecontainers, minor resistances are difficult to avoid if the containerswrinkle or are constricted by adjacent components, so implementing arelatively large flow resistance reduces differences in filling ordraining. This added resistance can also serve to limit flow betweenbladders as in Solution A. FIG. 12 is a diagram that shows an evendistribution of flow through a manifold using flow restrictions system110 and multiple fluid containers 102 a-c, which shows that addingrelatively large value resistance to parallel flow lines reduces theeffect of minor differences using variable innate flow resistance 112a-c and added identical flow restrictors 114 a-c in series,respectively.

Solution C—Balanced Reactant-to-Waste Transfer by Interleaved Bladders.

When each reactant solution is stored in its own separate space, the CGof each section is in the centroid of the fluid volume. Depending on therelative densities and volumes of each reactant, the combined CG of thereactants may not be in the centroid of the combined fluid volume. Onceall the reactants are consumed and converted to waste, if the waste isevenly distributed in the volume vacated by the consumed reactants, theCG of the waste will be at the centroid of the fluid volume because onlya single fluid exists at that point. This movement in CG may exceed theoperational limits of the vehicle or other system using the powersystem.

To avoid CG movement from the beginning of power production until allreactants are consumed, the layout of reactants should be symmetrical.This can be accomplished by dividing the reactants into multiplecontainers and alternating them in the layout. Waste containers situatedbetween the reactant bladders allow waste to fill the space vacated bythe reactants and keeps a constant horizontal CG location regardless ofwaste density. FIG. 13 is a diagram that shows an asymmetric layoutresults in horizontal CG shift if reactants are not of similar densityand/or volume. Subdividing containers for a symmetric layout maintains aconstant horizontal CG location.

Solution D—Pancake and Side-By-Side Bladder Configurations.

Specifically in reference to cylindrical reactant/waste containervolumes, two different collapsible container (bladder) layouts eachoffer unique features to address implementation concerns.

The first configuration is composed of “pancake” bladders, stackedback-to-back along the axis of the cylinder. This layout permits smalldeflection of each individual bladder, resulting in predictable collapseand inflation geometry. It also permits implementation of Solution A(multiple bladders as baffles) and Solution C (symmetric layout) tominimize movement of the reactant/waste CG. The narrow aspect ratio alsohelps collect any offgas in the top of each bladder for ventilationpurposes. The pancake design is amenable to other profiles, as well,since the overall shape can be fabricated to fit the geometry of theavailable space. Fabrication is straightforward since the bladders canbe formed from two flat panels, sealed together around the perimeter.FIG. 14 is a diagram that shows a “pancake” bladder configuration 120with alternating reactant/waste pairs 122. Suspension eyelets 124 aredepicted that permit the bladders to be aligned on a frame (notdepicted). Also shown are vent port(s) 126 and fill/drain ports 128. Forexample, the “pancake” bladder configuration 120 is depicted withalternating reactant/waste pairs 122, which alternate as follows: NaBH₄storage, Waste Storage, H₂O₂ storage, and waste storage, therebyproviding gravity balance during operation of the “pancake” bladderconfiguration 120 system and the overall system, and the reactants areexpended at about the same rate as the waste is generated.

The second configuration is useful when fluid densities and volumes aresimilar enough that CG shifting along the cylinder axis is not aconcern. This layout places bladders side-by-side along the axis of thecylinder. The orientation of the bladders parallel to the cylinder wallis conducive to the bladder filling the available volume. The reason forthis is when a two-panel flat container is inflated, it tends to assumea round shape due to the even pressure of the contents applied to thecontainer wall. For a rectangular bladder in a cylindrical space, thismeans the bladder will naturally conform to the inside diameter of thecylinder. The two primary benefits of this approach are 1) moreefficient use of space for reactant storage, and 2) the cylindersupports the bladder, reducing stress on the bladder wall. Since theshape readily fills the volume, the number of bladders required to usethe space effectively is reduced. A single bladder could fill thecylindrical volume, but lateral symmetry is lost by having a singlereactant container and a single waste container side-by-side. Tomaintain symmetry, two reactant bladders and two waste bladders can besituated on either side of the middle dividing line. A secondary benefitof this approach is it allows objects to extend through the middle ofthe reactant storage space, such as reinforcing tie-rods for the ends ofthe surrounding container, or for cables, tubing, or a conduit. FIG. 15is a diagram that shows side-by-side bladder configuration with reactantin purple and waste in orange (exploded view). Gray cylinder is forbladder installation and shows conduit passing through center.

Filling process optimization. Aside from physical configuration of thebladders and tanks, taking specific process steps can help withbalancing and maximizing fill volumes.

The first step to maximize fill volume and even distribution is topre-inflate the bladders with gas. The chief advantage of the gaspre-fill is that the weight of the gas does not restrict the motion ofthe bladders as they expand. When filling an empty bladder (gas removedby vacuum) the liquid tends to run to the bottom. As the liquid weightbuilds, it causes the bladder to sag and may trap bladder material atthe bottom of the tank, limiting its ability to expand upward andoutward. Pre-filling with gas expands the bag without sagging.Subsequently, the reactants can be filled while gas is removed from theheadspace via a vent at the same volumetric rate, thereby maintainingthe optimum form of the bladder.

With the side-by-side bladder configuration, filling the interiorbladders with reactants produces the most desirable result for spaceutilization. During the gas prefill, the interior bladders expand andflatten the exterior bladders against the outer wall of the tank. Thecollapsed bladders are designed to fit against the tank wall, sowrinkling and bunching are minimized. If the outer bladders are filledfirst, the inner bladders must crumple due to their excess material inthe middle. This can result in voids and reduced tank volumeutilization.

Bladder Gas Head Management.

As reactants and waste decompose, they generate gas. As this gasaccumulates in the top of the bladders, it begins to pressurize thebladders and may lead to leaks or bursting. To relieve the gas build-up,vents are located high in the bladders. These vents are protected byhydrophobic, gas-permeable membranes to allow gas to escape whileretaining liquids in the bladders. One embodiment of the vent is a smallcircular port mounted in the side of the bladder. This port functionseffectively when the container volume is sufficiently oversized to allowa gas head to build up before significant pressure accumulates. If theliquid level rises above the vent, gas cannot escape, so any volumeabove the vent is not available for reactant storage. Additionally, thevent must be above the liquid level in all orientations experienced bythe container for extended periods. Depending on the bladder design, itmay not be desirable or possible to locate this port at the very top ofthe bladder. Finally, the vent area is limited by the size of the port,which can cause undesired gas flow restriction, prevent off-gas fromescaping fast enough, or extend refueling times.

An improved gas vent is formed by locating a perforated tube in the topof the bladder and covering this tube in hydrophobic, gas-permeablemembrane. This vent is superior to a single port because it can belocated in the extremes of the bladder and service multiple positions,so that the high points in multiple orientations always have access tothe vent. Since it can access the high points more effectively, morevolume can be used for liquid storage rather than wasted as gasheadspace. Additionally, the vent area is no longer limited to the portsize, so a larger vent area can be provided to reduce gas flowrestriction. This vent can be mounted internally in the bladder duringfabrication using loops, clips or other standard means, but installationmay be desired after the bladder is formed. Placing a wire inside theperforated tube allows it to be shaped and held in the proper locationafter inserting it through a small port, permitting installation,removal, and replacement without cutting or replacing the bladder. FIG.16 is a cross-sectional side view of a perforated tube vent system 150with internal stiffener that can be installed through a small port andconfigured for best access to high points in the container for gasremoval. Alternatively to an internal stiffener, the perforated tube maybe selected from material with plastic or elastic deformation propertiesthat allow it to maintain position inside the bladder. The bladder wallis depicted into which a pass-through fitting 152 is attached thatconnects to the outside of the bladder. Inside the bladder theperforated tube vent system 150 includes a perforated tube 154 intowhich a wire 156 is inserted. A gas permeable film 158 surrounds theperforated tube 154 through which gas can flow.

The reaction of alkali and alkali-earth metal hydrides with water can beused for the generation of hydrogen. A non-limiting list of hydrides (inan aqueous solution) for use with the present invention are the ternaryhydrides including LiAlH₄, NaAlH₄, LiBH₄ and NaBH₄. Other ternaryhydrides, such as Mg(AlH4)₂ and liquid Al(BH₄)₃, can also be used withthe present invention. Lithium, sodium and magnesium react directly withhydrogen, under commercially convenient pressures and temperatureconditions, to form the binary metal hydrides LiH, NaH, and MgH₂.

Hydrogen Generation System. Sodium borohydride has high gravimetrichydrogen storage (amount of H₂ produced per unit weight of materials).Borate is formed as a byproduct when sodium borohydride undergoeshydrolysis to release hydrogen. Depending on conditions such astemperature and pressure, the borate's solubility can lead to theformation of undesirable solids unless due consideration is given. Thesesolids can produce inefficiencies in reactor function, which negativelyaffects hydrogen generation. The present invention includes a continuousH₂ generator system to produce maximum hydrogen output using the highesteffective storage concentration of sodium borohydride and, avoidingconditions where borate becomes insoluble. FIG. 17 is an embodiment ofthe hydrogen generator invention 901. The aqueous NaBH₄ is kept in oneor more storage reservoirs 902. The preferred hydride storageconcentration is between 10 and 30 wt %, preferably between 20 and 25%wt % for storage temperatures as low as 0° C. The expanded range isstill viable for storage temperatures down to ˜5° C. However, below thistemperature, the upper limit of 30% has converged with the solubilitylimit, thus dramatically increasing the likelihood of precipitateformation within the stored NaBH₄. The NaBH₄ catalytic hydrolysisreactor 903 contains specialized catalysts with a high surface area thatfavor the hydrolysis of NaBH₄. The reactor allows flow of NaBH₄ solutionthrough the reactor while retaining catalyst within the reactor beds.Additional water for the reaction (Eq 1) comes from a water reservoir904. Water in the reservoir is supplied from several sources including(1) “oxidizer water” 905 from the oxidant production subsystem (Eq 3)(2) water 906 from a fuel cell (Eq 4) and (3) from water recovered fromthe output stream 907 of the catalytic hydrolysis reactor. Water issupplied from these sources to the water reservoir via fluid conduits.As the water in the reservoir is depleted, from use in the hydrogengeneration system, the water is replenished at an equivalent rate withwater from the aforementioned sources.

Transfer of water and fuel from the storage reservoirs and into thehydrolysis reactor is via two separate pumps and conduit system thatmanages the reactant mixing flow regime into the catalytic reactor 910.In addition to pumps, conduit system 910 can contain, flow meters,pressure sensing devices, mixing zones, and check valves, as describedlater. The transfer pumps for water and fuel into the hydrolysis reactorare under variable control and are critical elements of the hydrogengenerator control architecture. Fluid transfer conduits between the fueland water reservoirs and the reactor incorporate bypass loops 911, 912.The bypass loops contains valves which divert flow away from the reactorand back into the original storage containers in short duration pulsesin order to clear the pumps of stalls in flow rate. The fuel solutiontends to have micro bubbles entrained in the liquid due to therelatively small rate of natural, unassisted hydrogen generation. Sodiumhydroxide is added to the NaBH₄ solution to stabilize the natural rateof NaBH₄ breakdown and hydrogen off gassing but gas production is noteliminated completely. The pump is appropriately sized to accommodateflow with only liquid against the expected reactor pressure at therequired flow rates. However, as the fuel pump encounters solution withbubbles, there is a risk of a stall in flow rate. Because the reactor iskept at a high pressure relative to the storage container, the pump hasto work harder to pump at a certain flow rate and the risk ofexperiencing stalls due to bubbles is increased. Once a stall isdetected by the flow meters, the bypass valves open momentarily to clearbubbles. By exposing the outlet of the pump to a lower pressure (storagecontainers), the pump is able to clear bubbles out of the pump headeasily so that when the outlet returns to the high pressure line thereis only liquid in the pump head and it can operate normally. Whilebubbles are more of a concern with the fuel solution, a bypass valve wasalso added to the water loop so that both pumps are protected fromstalls due to bubbles.

A high temperature phase separator is used to separate H₂ gas from aliquid 913. The residual liquid product contains dissolved NaBO₂ 914.The gas and liquid exiting the catalytic hydrolysis reactor is 915 at atemperature of ˜60 to 180° C. The separated liquid is recovered via adrain mechanism 916 and is sent to waste bladder storage as describedelsewhere in this application 917. Separated gas subsequently flows to aheat exchanger 918 where it is cooled to 60° C. At this point in thescheme a back pressure regulator is used 919. Condensed water isrecovered by the low temperature phase separator 920 via a drainmechanism and is then delivered to the water reservoir. Stored H₂ isdelivered to a fuel cell as needed from a H₂ accumulator 921. A forwardpressure regulator 922 is included to adjust the H₂ to the desiredpressure for the fuel cell 923. Product water from the fuel cell can besupplied via a conduit to the water reservoir 904.

The hydrogen generation system in FIG. 17 contains multiple pressurecontrolled zones. One pressure zone comprises the conduits between thewater reactor 904, fuel reactor 902 and the hydrolysis reactor 903.These zones are maintained typically at 55 psia.

A second pressure controlled zone is achieved through back pressureregulator 919. The pressurized zone extends from the hydrolysis reactoroutlet to the HT phase separator 913, through conduits 915, and heatexchanger conduits within 918. The pressure in this zone is controlledbetween 0 psig and 200 psig depending on the reaction conditions. Forexample, setting this zone to a higher pressure improves boratesolubility. Pressure in this zone setting may be varied via 919 inrelation to the reactor preheat temperature to achieve optimalhydrolysis reactor conditions.

Another pressure controlled zone comprises the LT phase separator 920and the hydrogen accumulator 921 and associated conduits. The pressureis controlled in a suitable range for delivery to the fuel cell 923.

Catalytic Reactor. The H₂ production reactor 903 is a flow-throughsingle pass design with unidirectional internal fluid flow, achievingcontinuous hydrogen output. The reactor design is given in FIG. 18.Light-weight design features are included. The middle screens hold thehydrolysis catalyst material 925. The number of screens can vary from 6to 60. Cartridge heaters allow temperature management and contribute torapid start up 924. There are 4 heaters (50 W capacity) total, with 2heaters inside each end plate. The reactor can be heated to 60° C. in <2minutes. The reactor's operation conditions require precise parametercontrol as described herein especially with regard to preheating of thereactor and reactor pressure.

The hydrolysis catalysts include a high surface area coating ofcobalt-boride on the expanded metal screen packages. The screen coatingprocedure first requires sonication for 30 minutes to remove any dirtand oil. After rinse the screens with large amounts of DI water, theyare soaked in a Woods Nickel Bath for at least 15 minutes. While thepackages are soaking, prepare the cobalt chloride solution. Move theWoods Nickel Bath to the 2L beaker and add a counter electrode connectedto a cathode power supply clip. Nickel plate the packages at 2.0V for 8seconds on each face. Thoroughly rinse off the plating solution from.Once the Cobalt Chloride solution has sat for 10 minutes, pour enoughsolution over the packages to half cover the top package with theplastic container tilted to keep the solution in the package corner.Slosh the solution to ensure that there are no pockets of DI water withno cobalt in it. Pour ⅓ to ½ as much of the NaBH₄ solution onto thescreens as the Cobalt Chloride Solution. Slosh the solution around,making sure to keep the packages covered with the solution, until bubbleformation stops. Rinse with DI water. Repeat several times in such a waythat the packages have been plated with the following sequence: nickel,cobalt, cobalt, nickel, cobalt, cobalt, nickel. The two later nickelcoats improve the adhesion of the cobalt and keep it from being torn offduring use. The packages should now be black and slightly fuzzy. Dry,wrap each package with a chem-wipe and store them in a plastic bag untilthey are used. Rough handling can break off the coating.

The reactor is designed and operated to achieve 100% hydrogenconversion. Conversion percentages are calculated by comparing the totalamount of H₂ produced through the duration of a test (according to amass flow meter) against the theoretical amount of hydrogen availablefrom the volume of NaBH₄ which was supplied to the reactor during adefined operation time, using Eq 1. for stoichiometry values requiredfor the calculation. The reactor as described herein provides a meansfor >95% and preferably 99.0 to 100.0% conversion, which means thereactor can achieve zero NaBH₄ or near zero NaBH₄ in the reactor outputstream. Another feature of the reactor is operation without formation ofcrystal (insoluble) NaBH₄ or NaBO₂ within the hydrogen productioncatalytic reactor or adjacent fluid conduits. Included in the design arepressure sensing and pressure control at designated points in the flowsystem. Cooling of the catalytic reactor is achieved through the controlarchitecture, by adjusting fluid flow rate through the reactor.Temperature sensing and control equipment items are included in thecatalytic reactor design. Pressure and sensor controls are used inconjunction with the variables described above to achieve conditions oftemperature and pressure, affecting water availability, and improvingthe solubility of NaBO₂ in the reactor and associated fluid conduits.

Fuel Management. Details of fluid management between fuel/water storageand hydrolysis reactor via the conduit system 910 are given in FIG. 19.A mixing zone 940 allows adequate dilution of the fuel from its storageconcentration to its use concentration. As the fuel and water pumps rampup and down during operation, the ratio of fuel to water will vary. Thepurpose of the mixing chamber is to provide a buffer for any abruptchanges in concentration that may occur. The system is preferablycontrolled at a concentration less than 12% NaBH₄. Assuming that allpoints in the reactor are at temperatures greater than 23° C., 12% canbe a safe upper limit to prevent formation of NaBO₂ solids in thereactor. Because the flow rates can change abruptly during pressure ondemand operation of the system, having this buffer volume to dilute anymomentary or periodic changes in concentration protects the reactor fromconditions, which could affect solubility. Fuel flow rate is controlledby the feedback from a pressure transducer 941. Pressure transducer canbe located at any position between the fuel solution reservoir 902 andreactor 903. The pressure transducer may be in close proximity to themixing zone 940. Goal is to maintain an accumulated pressure of 55 psiaat pressure transducer 941. The conduit between the fuel reservoir andthe mixing zone 940 can include a bypass valve 912, pump 942, flow meter943, check valve 944. The conduit between the water reservoir 904 andthe mixing zone 940 can include a bypass valve 911, pump 945, flow meter946, and a check valve 947.

Because this is a pressure on demand system, but there is a slight delaybetween the fuel flow rate and hydrogen generation, an accumulatorvolume 921 was added after the low temperature phase separator 920. Asthe demand for hydrogen fluctuates up and down, the accumulated volumeprovides a consistent supply of hydrogen pressure for the fuel cell. Thepressure in the accumulator 921 is monitored by pressure transducer 926and maintained in the range of 35-75 psia by increasing or decreasingthe flow rate of the fuel solution into the reactor 903 via fuel pump924. Pressure transducer 926 is in communication with accumulator volume921. The lower pressure limit (35 psia) ensures that the pressure alwaysstays above the pressure required by the fuel cell 923. A typicalpressure required by the hydrogen feed to the fuel cell is 25 psi. Theaccumulator helps to ensure the fuel cell is never starved of sufficienthydrogen.

The upper limit of 75 psia prevents excessive production of hydrogen andrisk of over pressurization of the system.

The control scheme ramps the fuel pump 942 up if pressure monitored by926 falls below 55 psia so that hydrogen generation can keep up with thefuel cell's hydrogen demand. The fuel pump ramps down when the demanddecreases and the 926 pressure rises above 55 psia, eventually shuttingoff the fuel pump if 75 psia is reached. The fuel pump 942 is controlledby the fuel flow rate and closed loop feedback from the fuel flow meter943. The goal is to maintain the required fuel flow rate as indicated bythe flow meter. For the optimum operation of ˜10% NaBH₄ and waterbalance (made up from: H₂O₂ product water; fuel cell water and reactorrecovered water) for a ˜900 W fuel cell output, the fuel solution feedrate should be preferably at ˜13 ml/min. During normal pressure ondemand operation, the flow rate range will be as low as 0 ml/min (zero)when the hydrogen production should slow down or stop, and as high as˜20 ml/min when the fuel cell is at higher power, needing a high rate ofhydrogen feed.

The water flow rate between reservoir 904 and mixing zone 940, isdirectly correlated to the fuel flow rate in order to maintain a NaBH₄concentration entering reactor 903 at <12% for solubility protectionand >8% so that water balance is maintained in a desirable range, suchthat the level of water in 904 is neither depleted or accumulated toexcess. To achieve a desired level of water in the reservoir, the waterflow rate between 904 and 940 is also controlled by feedback from thewater reservoir electronic level sensor. The reservoir electronic levelsensor provides feedback to pump 945 enabling the pumping rate to beadjusted. The goal is to maintain a reservoir water level at or near toa set volume. Because this measurement has direct correlation to thewater balance, if all the systems are functioning optimally, the waterlevel should be maintained at or near a constant level. However, slightdeviations from a completely balanced system could compound over longterm operation and the water reservoir could deplete or overfill. If lowwater level is detected by the electronic sensor, there is a need toavoid the water pump being starved of supply and the fuel solution notbeing sufficiently diluted. Thus, the control scheme operates accordingto the electronic level sensor. The control scheme decreases the waterflow rate via pump 945 so that the water consumption is slower while theinput water to the reservoir (from: oxidizer product water; fuel cellwater; reactor recovered water) replenishes the reservoir to the desiredlevel. If the level is rising, the water flow rate via pump 945 isincreased to prevent overflow of the reservoir. For a fuel celloperating at ˜900 W, a preferred NaBH₄ concentration entering thereactor is ˜10% NaBH₄ (the storage concentration of NaBH₄ fuel is 25%).The flow rate into the reactor is ˜23 ml/min. The fuel flow rate between902 and 940 can be as low as 0 ml/min when hydrogen demand decreases oras high as ˜30 ml/min when hydrogen demand is high.

Water flow rate from 904 to the reactor 903 via 940 is also preferablyhigh when the reactor is being shut down. During shut down, the fuelpump 942 is turned off and water is used to flush the reactor ofresidual fuel solution as well as cool the reactor to room temperature.

Reactor Water Recovery by Phase Separation FIG. 20A is the configurationof the first stage high temperature phase separator 913. This hightemperature phase separator has the inlet from 903 above the water line.The temperature of the hydrogen containing gas/fluid from reactor 903 istypically 110-130° C. The liquid waste is separated from the gas streamby gravity and the gas stream continues downstream via conduit 915 tothe heat exchanger 918. The liquid waste in the separator typically isat 90° C. The liquid waste is transferred to waste bladders 917described elsewhere in this application. According to the controlscheme, the drain valve 916 opens once the water level in the separatorreaches a predetermined point. The water level in the separator chamberis monitored by a continuous operating electronic sensor. A float-typesensor may be used 927.

The gas stream exits the heat exchanger 918, it continues to the lowtemperature separator 920 where the condensed water is separated fromthe hydrogen-containing gas stream. FIG. 20B gives the configuration ofthe low temperature phase separator. The condensed water from 920 isrecovered via 907 and 908 and fed to the water reservoir 904. Inaddition to capturing condensed water, the separator also captures microparticles in the stream by using a sparger to divide the stream intosmall bubbles, which pass through liquid water in the separator. Inorder to incorporate the sparger into the separator 928, the separatorbody is configured so that the inlet will remain below the water lineand a stainless steel filter is fitted into the inlet. According to thecontrol scheme, the drain valve 907 opens once the water level in theseparator reaches a predetermined set point. The water level in theseparator chamber is monitored by an electronic sensor. A float-typesensor may be used 929.

Water Reservoir. FIG. 21A shows the design of the water reservoir 904and the means of water recovery. The byproduct water from the oxidizer,fuel cell, and the recovered water reactor will fill the waterreservoir, following which the water will be used to supply the fueldilution water pump 945. The reservoir will also be vented with a Gorebrand PTFE membrane which allows gas to flow freely in and out of thereservoir while preventing liquid from exiting the reservoir 930. Thiswill allow the container to remain unpressurized throughout the durationof the mission. Furthermore, a differential pressure transducer 931 willbe used in order to determine the difference between the water columnpressure at the bottom of the reservoir and the pressure in theheadspace of the reservoir, and the differential pressure will be usedto calculate the water level. Alternatively a float type continuouslevel sensor 932 can be used to increase reliability and make the levelsensing more robust see FIG. 21B. Under ideal conditions, the waterlevel in the reservoir should not fluctuate, but if the water level isrising or falling over time, the water pump will slightly ramp up ordown to account for minor differences that may occur between the inletand outlet flow rates. This will help to eliminate an excessively lowwater level which would deprive the dilution pump or a high water levelwhich could pressurize the container and lead to failure.

Example 1 includes one set of operating conditions and parameters forthe continuous H₂ generating system.

EXAMPLE 1 INPUT TO REACTOR NaBH₄ storage concentration 25 wt % NaBH₄flow rate ~13 mL/min H₂O flow rate ~23 mL/min NaBH₄ feed concentration~10 wt % REACTOR CONDITIONS Temperature 125° C. Pressure 75 psiaInsoluble NaBO₂ formation No Insoluble NaBH₄ No Residence time ~17 sOUTPUT FROM REACTOR H₂ flow rate ~8.0 slpm H₂ purity 99.999% H₂conversion   100% Insoluble NaBO₂ No NaBH₄ output concentration <0.05 wt% NaBO₂ output concentration 17.3 wt %

Example 2 includes another set of operating conditions and parametersfor the continuous H₂ generating system. In this configuration thereactor can be operated with no pre-heating but pressurized.

REACTOR CONTROLS Reactor Inlet Feed Temperature 20 C. Reactor BackPressure Control 60 psig NaBH₄ feed concentration 10 wt % RESULTANTOPERATIONAL CONDITIONS Reactor Outlet Temperature 114 C. Outlet WaterVapor Quality 10% NaBO₂ concentration 19 wt % NaBO₂ Solubility 21 wt %Insoluble NaBO₂ formation No

Example 3 shows some of the values for preheating temperature and lowvalues for the back pressure setting leads to borate insolubility. Inthis configuration the reactor can be operated with no pre-heating orpressure.

REACTOR CONTROLS Reactor Inlet Feed Temperature 20 C. Reactor BackPressure Control 0 psig NaBH₄ feed concentration 10 wt % RESULTANTOPERATIONAL CONDITIONS Reactor Outlet Temperature 79 C. Outlet WaterVapor Quality 18% NaBO₂ concentration 21 wt % NaBO₂ Solubility 21 wt %Insoluble NaBO₂ formation Yes

Examples 4 includes another set of operating conditions and parametersfor the continuous H₂ generating system when the concentration of NaBH₄entering the hydrolysis reactor 20 wt %. With high NaBH₄ inletconcentrations, both pre-heating and an increase in pressure are needed.In this configuration the reactor can be operated with pre-heating andpressurization.

REACTOR CONTROLS Reactor Inlet Feed Temperature 70 C. Reactor BackPressure Control 200 psig NaBH₄ feed concentration 20 wt % RESULTANTOPERATIONAL CONDITIONS Reactor Outlet Temperature 166 C. Outlet WaterVapor Quality 54 wt % NaBO₂ concentration 55 wt % NaBO₂ Solubility 56 wt% Insoluble NaBO₂ formation No

Example 5 shows another embodiment of operating conditions. Preheatingis applied but the back pressure regulator is set at a low pressure.These conditions in borate insolubility. In this configuration thereactor can be operated with pre-heating but not pressurized.

REACTOR CONTROLS Reactor Inlet Feed Temperature 70 C. Reactor BackPressure Control 0 psig NaBH₄ feed concentration 20 wt % RESULTANTOPERATIONAL CONDITIONS Reactor Outlet Temperature 85 C. Outlet WaterVapor Quality 77 wt % NaBO₂ concentration 71 wt % NaBO₂ Solubility 56 wt% Insoluble NaBO₂ formation Yes

Example 6 shows yet another set of operating conditions. It uses a NaBH₄entering the hydrolysis reactor 20 wt %. The backpressure control is setat a high value. However, the inlet temperature is set at a low value.These conditions result in borate insolubility. In this configurationthe reactor can be operated with no pre-heating but pressurized.

REACTOR CONTROLS Reactor Inlet Feed Temperature 20 C. Reactor BackPressure Control 200 psig NaBH₄ feed concentration 20 wt % RESULTANTOPERATIONAL CONDITIONS Reactor Outlet Temperature 160 C. Outlet WaterVapor Quality 41 wt % NaBO₂ concentration 49 wt % NaBO₂ Solubility 21 wt% Insoluble NaBO₂ formation Yes

Example 7 includes another set of operating conditions and parametersfor the continuous H₂ generating system when the concentration of NaBH₄entering the hydrolysis reactor 10 wt %. In this configuration thereactor can be operated with pre-heating but not pressurized.

REACTOR CONTROLS Reactor Inlet Feed Temperature 30 C. Reactor BackPressure Control 0 psig NaBH₄ feed concentration 10 wt % RESULTANTOPERATIONAL CONDITIONS Reactor Outlet Temperature 80 C. Outlet WaterVapor Quality 20 wt % NaBO₂ concentration 21 wt % NaBO₂ Solubility 26 wt% Insoluble NaBO₂ formation No

FIGS. 22A and 22B are graphs that show the product as a weight percentwt % of the NaBH₄ and NaBO₂, in relation to: FIG. 22A the wt % ofreactant NaBH₄, and in FIG. 22B the wt % of the reactant H₂O₂.

It is contemplated that any embodiment discussed in this specificationcan be implemented with respect to any method, kit, reagent, orcomposition of the invention, and vice versa. Furthermore, compositionsof the invention can be used to achieve methods of the invention.

It will be understood that particular embodiments described herein areshown by way of illustration and not as limitations of the invention.The principal features of this invention can be employed in variousembodiments without departing from the scope of the invention. Thoseskilled in the art will recognize, or be able to ascertain using no morethan routine experimentation, numerous equivalents to the specificprocedures described herein. Such equivalents are considered to bewithin the scope of this invention and are covered by the claims.

All publications and patent applications mentioned in the specificationare indicative of the level of skill of those skilled in the art towhich this invention pertains. All publications and patent applicationsare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually indicated to be incorporated by reference.

The use of the word “a” or “an” when used in conjunction with the term“comprising” in the claims and/or the specification may mean “one,” butit is also consistent with the meaning of “one or more,” “at least one,”and “one or more than one.” The use of the term “or” in the claims isused to mean “and/or” unless explicitly indicated to refer toalternatives only or the alternatives are mutually exclusive, althoughthe disclosure supports a definition that refers to only alternativesand “and/or.” Throughout this application, the term “about” is used toindicate that a value includes the inherent variation of error for thedevice, the method being employed to determine the value, or thevariation that exists among the study subjects.

As used in this specification and claim(s), the words “comprising” (andany form of comprising, such as “comprise” and “comprises”), “having”(and any form of having, such as “have” and “has”), “including” (and anyform of including, such as “includes” and “include”) or “containing”(and any form of containing, such as “contains” and “contain”) areinclusive or open-ended and do not exclude additional, unrecitedelements or method steps. In embodiments of any of the compositions andmethods provided herein, “comprising” may be replaced with “consistingessentially of” or “consisting of”. As used herein, the phrase“consisting essentially of” requires the specified integer(s) or stepsas well as those that do not materially affect the character or functionof the claimed invention. As used herein, the term “consisting” is usedto indicate the presence of the recited integer (e.g., a feature, anelement, a characteristic, a property, a method/process step or alimitation) or group of integers (e.g., feature(s), element(s),characteristic(s), propertie(s), method/process steps or limitation(s))only.

The term “or combinations thereof” as used herein refers to allpermutations and combinations of the listed items preceding the term.For example, “A, B, C, or combinations thereof” is intended to includeat least one of: A, B, C, AB, AC, BC, or ABC, and if order is importantin a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.Continuing with this example, expressly included are combinations thatcontain repeats of one or more item or term, such as BB, AAA, AB, BBC,AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan willunderstand that typically there is no limit on the number of items orterms in any combination, unless otherwise apparent from the context.

As used herein, words of approximation such as, without limitation,“about”, “substantial” or “substantially” refers to a condition thatwhen so modified is understood to not necessarily be absolute or perfectbut would be considered close enough to those of ordinary skill in theart to warrant designating the condition as being present. The extent towhich the description may vary will depend on how great a change can beinstituted and still have one of ordinary skilled in the art recognizethe modified feature as still having the required characteristics andcapabilities of the unmodified feature. In general, but subject to thepreceding discussion, a numerical value herein that is modified by aword of approximation such as “about” may vary from the stated value byat least ±1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.

All of the compositions and/or methods disclosed and claimed herein canbe made and executed without undue experimentation in light of thepresent disclosure. While the compositions and methods of this inventionhave been described in terms of preferred embodiments, it will beapparent to those of skill in the art that variations may be applied tothe compositions and/or methods and in the steps or in the sequence ofsteps of the method described herein without departing from the concept,spirit and scope of the invention. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope and concept of the invention as defined by theappended claims.

What is claimed is:
 1. An apparatus for volumetric and gravimetric storage of reactants and waste of an integrated fuel cell system comprising: one or more reactant or fuel storage bladders; and one or more waste storage bladders, wherein the reactant or fuel storage bladders and the waste storage bladders form a stack of bladders, and the stack of bladders are interleaved between the reactant or fuel storage bladders and the waste storage bladders, such that both a volumetric and a gravimetric balance is maintained as reactant or fuel are used and the waste bladder is filled.
 2. The apparatus of claim 1, wherein the bladders are plastic, polymer, rubber, thermoplastic, composite, silicone, fiberglass, or carbon fiber.
 3. The apparatus of claim 1, wherein the stack of bladders is conformal with a container that at least partially encloses the stack of bladders.
 4. The apparatus of claim 1, wherein the reactant or fuel storage bladders and/or the waste storage bladders are selected from a material capable of storing corrosive, acid, basic, external pressure, internal pressure, cold, heat, UV protected, chemical solvents, organic solvents, mineral solvents, radioactive elements or compounds, or oxidation.
 5. The apparatus of claim 1, wherein the reactant or fuel storage bladders and/or the waste storage bladders further comprise a liner, wherein the liner is selected from polytetrafluoroethylene, metal, plastic, carbon fiber, glass fiber, a material substantially impermeable to gases, a material substantially permissive of gas diffusion, or selective gas diffusion.
 6. The apparatus of claim 1, wherein the reactant or fuel storage bladders and/or the waste storage bladders area at least partially rigid.
 7. The apparatus of claim 1, wherein the reactant or fuel storage bladders and/or the waste storage bladders are defined further as comprising a heat sink.
 8. The apparatus of claim 1, further comprising a reinforcing material in, within, or on the reactant or fuel storage bladders and/or the waste storage bladders selected from carbon fiber, metal, polymeric, nylon, a para-aramid synthetic fiber, a natural fiber, wood, or bamboo.
 9. The apparatus of claim 1, wherein the reactant or fuel storage bladders and/or the waste storage bladders is cylindrical, ovoidal, pancake shaped, accordion shaped, tubular, polygonal, cubic, spherical, pyramidal, rhomboid, conical, half-cylinders that sandwich an expandable bladder, vessel, or container.
 10. The apparatus of claim 1, wherein the reactant or fuel storage bladders and/or the waste storage bladders further comprise one or more baffles within the reactant or fuel storage bladders and/or the waste storage bladders.
 11. The apparatus of claim 1, further comprising one or more flow restrictors between the two or more reactant or fuel storage bladders and/or the two or more waste bladders to dampen fluid movement in the two or more reactant or fuel storage bladders and/or the two or more waste bladders during operation.
 12. The apparatus of claim 1, wherein the reactant storage bladders comprise, independently, a NaBH₄ storage bladder and a H₂O₂ storage bladder.
 13. The apparatus of claim 1, wherein a reactant for use in the fuel cell system is a metal-hydride.
 14. The apparatus of claim 1, wherein a reactant for use with the present invention is selected from at least one of NaBH₄, LiBH₄, KBH₄, Ca(BH₄)₂, or Mg(BH₄)₂.
 15. A method of maintaining a volumetric and gravimetric balance in a closed system comprising: providing two or more reactant or fuel storage bladders and one or more waste bladders; and forming a stack of bladders by interleaving the two or more storage or fuel storage bladders and the one or more waste bladders, wherein a volumetric and a gravimetric balance is maintained as reactant or fuel is used and the waste bladder is filled.
 16. The method of claim 15, further comprising connecting the two or more the reactant or fuel storage bladders to a reactor inlet and a fuel cell, and connecting the reactor fuel outlet and/or a fuel cell outlet to the one or more waste bladders and adapting the closed system to fit into an unmanned underwater vehicle.
 17. The method of claim 15, wherein the bladders are plastic, polymer, rubber, thermoplastic, composite, silicone, fiberglass, or carbon fiber.
 18. The method of claim 15, wherein the stack of bladders is conformal with a container that at least partially encloses the stack of bladders.
 19. The method of claim 15, wherein the reactant or fuel storage bladders and/or the waste storage bladders are selected from a material capable of storing corrosive, acid, basic, external pressure, internal pressure, cold, heat, UV protected, chemical solvents, organic solvents, mineral solvents, radioactive elements or compounds, or oxidation.
 20. The method of claim 15, wherein the reactant or fuel storage bladders and/or the waste storage bladders further comprise a liner, wherein the liner is selected from polytetrafluoroethylene, metal, plastic, carbon fiber, glass fiber, a material substantially impermeable to gases, a material substantially permissive of gas diffusion, or selective gas diffusion.
 21. The method of claim 15, wherein the reactant or fuel storage bladders and/or the waste storage bladders area at least partially rigid.
 22. The method of claim 15, wherein the reactant or fuel storage bladders and/or the waste storage bladders are defined further as comprising a heat sink.
 23. The method of claim 15, further comprising a reinforcing material in, within, or on the reactant or fuel storage bladders and/or the waste storage bladders selected from carbon fiber, metal, polymeric, nylon, a para-aramid synthetic fiber, a natural fiber, wood, or bamboo.
 24. The method of claim 15, wherein the reactant or fuel storage bladders and/or the waste storage bladders is cylindrical, ovoidal, pancake shaped, accordion shaped, tubular, polygonal, cubic, spherical, pyramidal, rhomboid, conical, half-cylinders that sandwich an expandable bladder, vessel, or container.
 25. The method of claim 15, wherein the reactant or fuel storage bladders and/or the waste storage bladders further comprise one or more baffles within the reactant or fuel storage bladders and/or the waste storage bladders.
 26. The method of claim 15, further comprising providing one or more flow restrictors between the two or more reactant or fuel storage bladders and/or the one or more waste bladders to dampen fluid movement in the two or more reactant or fuel storage bladders and/or the one or more waste bladders during operation.
 27. The method of claim 15, further comprising the step of maximizing a fill volume and even distribution of one or more reactants by pre-inflating the two or more reactant or fuel storage bladders with gas.
 28. The method of claim 27, further comprising the step of filling the two or more reactant or fuel storage bladders with reactants while the gas is removed from a headspace via a vent in the two or more reactant or fuel storage bladders at the same volumetric rate, thereby maintaining an optimum form for the bladder.
 29. The method of claim 15, wherein a reactant for use in the fuel cell system is a metal-hydride.
 30. The method of claim 15, wherein a reactant for use with the present invention is selected from at least one of NaBH₄, LiBH₄, KBH₄, Ca(BH₄)₂, or Mg(BH₄)₂.
 31. A method of operating an underwater vehicle comprising: an underwater vehicle comprising one or more reactant or fuel storage bladders; and maintaining a volumetric and gravimetric balance in a closed system by: providing two or more the reactant or fuel storage bladders and one or more waste bladders; and forming a stack of bladders by interleaving the two or more storage or fuel storage bladders and the one or more waste bladders, wherein a volumetric and a gravimetric balance is maintained as reactant or fuel is used and the waste bladder is filled.
 32. A gas vent for use with a bladder system comprising: a perforated tube that extends inside a bladder; a gas permeable film that surrounds the perforated tube and covers substantially all of the perforation in the perforated tube; a pass-through fitting that is attachable to a wall of the bladder, wherein gas in the bladder traverses the gas permeable membrane, though the perforations in the tube and through the pass-through fitting to exit the bladder.
 33. The gas vent of claim 32, wherein the pass-through fitting has a 30, 45, 60, 75, 90, 105, 120, 135, 150, or 165 degree angle.
 34. The gas vent of claim 32, wherein the gas permeable membrane is selected to only permit certain types of gases to enter the perforated tube and/or to prevent liquids from exiting the bladder.
 35. The gas vent of claim 32, wherein the gas permeable membrane is hydrophobic.
 36. The gas vent of claim 32, wherein the perforated tube is a self-supporting tube, and/or is supported by a wire or stiffener inserted in the perforated tube that provides mechanical rigidity to the perforated tube and can be shaped accordingly.
 37. The gas vent of claim 32, further comprising a pressure valve connected between the perforated tube and an outlet of the gas vent to prevent escape of a gas until a certain internal pressure is reached within the bladder.
 38. The gas vent of claim 32, wherein the gas vent eliminates the need for head space in a bladder for gas, while retaining liquids. 